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Control of Porphyrin Planarity and Aggregation by Covalent Capping: Bissilyloxy Porphyrin Silanes

Hussein, B.A.; Shakeel, Z.; Turley, A.T.; Bismillah, A.N.; Wolfstadt, K.; Pia, J.; Pilkington, M.; McGonigal, P.R.; Adler, M.

Control of Porphyrin Planarity and Aggregation by Covalent Capping: Bissilyloxy Porphyrin Silanes Thumbnail


Authors

B.A. Hussein

Z. Shakeel

A.T. Turley

A.N. Bismillah

K. Wolfstadt

J. Pia

M. Pilkington

M. Adler



Abstract

Porphyrins are cornerstone functional materials that are useful in a wide variety of settings, ranging from molecular electronics to biology and medicine. Their applications are often hindered, however, by poor solubilities that result from their extended, solvophobic aromatic surfaces. Attempts to counteract this problem by functionalizing their peripheries have been met with only limited success. Here, we demonstrate a versatile strategy to tune the physical and electronic properties of porphyrins using an axial functionalization approach. Porphyrin silanes (PorSils) and bissilyloxy PorSils (SOPS) are prepared from porphyrins by operationally simple κ4N-silylation protocols, introducing bulky silyloxy “caps” that are central and perpendicular to the planar porphyrin. While porphyrins typically form either J- or H-aggregates, SOPS do not self-associate in the same manner: the silyloxy axial substituents dramatically improve the solubility by inhibiting aggregation. Moreover, axial porphyrin functionalization offers convenient handles through which optical, electronic, and structural properties of the porphyrin core can be modulated. We observe that the identity of the silyloxy substituent impacts the degree of planarity of the porphyrin in the solid state as well as the redox potentials.

Citation

Hussein, B., Shakeel, Z., Turley, A., Bismillah, A., Wolfstadt, K., Pia, J., …Adler, M. (2020). Control of Porphyrin Planarity and Aggregation by Covalent Capping: Bissilyloxy Porphyrin Silanes. Inorganic Chemistry, 59(18), 13533-13541. https://doi.org/10.1021/acs.inorgchem.0c01891

Journal Article Type Article
Acceptance Date Aug 12, 2020
Online Publication Date Aug 30, 2020
Publication Date 2020
Deposit Date Aug 13, 2020
Publicly Available Date Aug 30, 2021
Journal Inorganic Chemistry
Print ISSN 0020-1669
Electronic ISSN 1520-510X
Publisher American Chemical Society
Peer Reviewed Peer Reviewed
Volume 59
Issue 18
Pages 13533-13541
DOI https://doi.org/10.1021/acs.inorgchem.0c01891
Related Public URLs https://chemrxiv.org/articles/Control_of_Porphyrin_Planarity_and_Aggregation_by_Covalent_Capping_Bissilyloxy_Porphyrin_Silanes/12195084

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Copyright Statement
This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see https://doi.org/10.1021/acs.inorgchem.0c01891







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